Global Dam‐Driven Changes to Riverine N:P:Si Ratios Delivered to the Coastal Ocean

River damming alters nutrient fluxes along the land-ocean aquatic continuum as a result of biogeochemical processes in reservoirs. Both the changes in riverine nutrient fluxes and nutrient ratios impact ecosystem functioning of receiving water bodies. We utilize spatially distributed mechanistic models of nitrogen (N), phosphorus (P), and silicon (Si) cycling in reservoirs to quantify changes in nutrient stoichiometry of river discharge to coastal waters. The results demonstrate that the growing number of dams decouples the riverine fluxes of N, P, and Si. Worldwide, preferential removal of P over N in reservoirs increases N:P ratios delivered to the ocean, raising the potential for P limitation of coastal productivity. By midcentury, more than half of the rivers discharging to the coastal zone will experience a higher removal of reactive Si relative to reactive P and total N, in response to the rapid pace at which new hydroelectric dams are being built

Global Controls on DOC Reaction Versus Export in Watersheds: A Damköhler Number Analysis

The relative capacity for watersheds to eliminate or export reactive constituents has important implications on aquatic ecosystem ecology and biogeochemistry. Removal efficiency depends on factors that affect either the reactivity or advection of a constituent within river networks. Here, we characterized Damköhler number (Da) for dissolved organic carbon (DOC) uptake in global river networks. Da equals the advection to reaction timescale ratio and thus provides a unitless indicator for DOC reaction intensity during transport within river networks. We aim to demonstrate the spatial and temporal patterns and interplays among factors that determine DOC uptake across global river networks. We show that watershed size imposes a primary control on river network DOC uptake due to a three orders of magnitude difference in water residence time (WRT) between the smallest and largest river networks. DOC uptake capacity in tropical river networks is 2–6 times that in temperate and the Arctic river networks, coinciding with larger DOC removals in warm than in cold watersheds. River damming has a profound impact on DOC uptake due to significantly extended WRTs, particularly in temperate watersheds where most constructed dams are situated. Global warming is projected to increase river network DOC uptake by ca. 19% until year 2100 under the RCP4.5 scenario

Effects of pH and Dissolved Silicate on Phosphate Mineral-Water Partitioning with Goethite

Release of sorbed phosphate from ferric iron oxyhydroxides can contribute to excessive algal growth in surface water bodies. Dissolved silicate has been hypothesized to facilitate phosphate desorption by competing for mineral surface sites. Here, we conducted phosphate and silicate adsorption experiments with goethite under a wide pH range (3–11), both individually (P or Si) and simultaneously (P plus Si). The entire experimental data set was successfully reproduced by the charge distribution multisite surface complexation (CD-MUSIC) model. Phosphate adsorption was highest under acidic conditions and gradually decreased from near-neutral to alkaline pH conditions. Maximum silicate adsorption, in contrast, occurred under alkaline conditions, peaking around pH 10. The competitive effect of silicate on phosphate adsorption was negligible under acidic conditions, becoming more pronounced under alkaline conditions and elevated molar Si:P ratios (>4). In a subsequent experiment, desorption of phosphate with increasing pH was monitored, in the presence or absence of dissolved silicate. While, as expected, desorption of phosphate was observed during the transition from acidic to alkaline conditions, a fraction of phosphate remained irreversibly bound to goethite. Even at high Si:P ratios and alkaline pH, dissolved silicate did not affect phosphate desorption, implying that kinetic factors prevented silicate from displacing phosphate from goethite binding sites

Lake Morphometry and River Network Controls on Evasion of Terrestrially Sourced Headwater CO₂

Lakes are central components of the inland water system distinct from, yet inextricably connected to, river networks. Currently, existing network-scale biogeochemistry research, although robust, typically treats each of these components separately or reductively. Here, we incorporate lake morphometry into a fully connected stream/lake network for the Connecticut River watershed and model potential evasion of terrestrially sourced headwater CO2 as transported through the network, ignoring in-stream production. We found that approximately 25%–30% of total potential soil CO2 evasion occurs in lakes, and percent evasion is inversely related to streamflow. A lake's ability to evade CO2 is controlled by residence time and size: most lakes with residence time over 7 days or surface area greater than 0.004 km2 evade functionally all terrestrial CO2 entering from upstream, precluding further downstream transport. We conclude that lakes are important for soil CO2 degassing and that this coupled river/lake approach is promising for CO2 studies henceforth

Does Photomineralization of Dissolved Organics Matter in Temperate Rivers?

Sunlight can oxidize dissolved organic carbon (DOC) to dissolved inorganic carbon (DIC) in freshwaters. The importance of complete photooxidation, or photomineralization, as a sink for DOC remains unclear in temperate rivers, as most estimates are restricted to lakes, high latitude rivers, and coastal river plumes. In this study, we construct a model representing over 75,000 river reaches in the Connecticut River Watershed (CRW), USA, to calculate spectrally resolved photomineralization. We test the hypothesis that photomineralization is a negligible DOC sink across all reaches and flow conditions relative to DOC fluxes. Our model quantifies reaction rates and transport drivers within the river reaches for the ranges of flow conditions, incoming solar irradiance, and canopy cover shading observed throughout the year. Our model predicts average daily areal photomineralization rates ranging from 1.16 mg-C m−2 day−1 in low flow river reaches in the winter, to 18.33 mg-C m−2 day−1 in high flow river reaches during the summer. Even for high photomineralization fluxes, corresponding photomineralization uptake velocities are typically at least an order of magnitude smaller than those reported for other instream processes. We calculate DOC elimination by photomineralization relative to DOC fluxes through individual stream reaches as well as the entire riverine portion of the CRW. We find that relative photomineralization fluxes are highest in summer drought conditions in low order streams. In median flows and mean light intensities, for an average watershed travel distance, 3%–5% of the DOC fluxes are eliminated, indicating that photomineralization is a minor DOC sink in temperate rivers

Increased nitrous oxide emissions from global lakes and reservoirs since the pre-industrial era

Lentic systems (lakes and reservoirs) are emission hotpots of nitrous oxide (N2O), a potent greenhouse gas; however, this has not been well quantified yet. Here we examine how multiple environmental forcings have affected N2O emissions from global lentic systems since the pre-industrial period. Our results show that global lentic systems emitted 64.6 ± 12.1 Gg N2O-N yr−1 in the 2010s, increased by 126% since the 1850s. The significance of small lentic systems on mitigating N2O emissions is highlighted due to their substantial emission rates and response to terrestrial environmental changes. Incorporated with riverine emissions, this study indicates that N2O emissions from global inland waters in the 2010s was 319.6 ± 58.2 Gg N yr−1. This suggests a global emission factor of 0.051% for inland water N2O emissions relative to agricultural nitrogen applications and provides the country-level emission factors (ranging from 0 to 0.341%) for improving the methodology for national greenhouse gas emission inventories

Hysteresis Patterns of Watershed Nitrogen Retention and Loss Over the Past 50 years in United States Hydrological Basins

Patterns of watershed nitrogen (N) retention and loss are shaped by how watershed biogeochemical processes retain, biogeochemically transform, and lose incoming atmospheric deposition of N. Loss patterns represented by concentration, discharge, and their associated stream exports are important indicators of integrated watershed N retention behaviors. We examined continental United States (CONUS) scale N deposition (e.g., wet and dry atmospheric deposition), vegetation trends, and stream trends as potential indicators of watershed N-saturation and retention conditions, and how watershed N retention and losses vary over space and time. By synthesizing changes and modalities in watershed nitrogen loss patterns based on stream data from 2200 U.S. watersheds over a 50 years record, our work revealed two patterns of watershed N-retention and loss. One was a hysteresis pattern that reflects the integrated influence of hydrology, atmospheric inputs, land-use, stream temperature, elevation, and vegetation. The other pattern was a one-way transition to a new state. We found that regions with increasing atmospheric deposition and increasing vegetation health/biomass patterns have the highest N-retention capacity, become increasingly N-saturated over time, and are associated with the strongest declines in stream N exports—a pattern, that is, consistent across all land cover categories. We provide a conceptual model, validated at an unprecedented scale across the CONUS that links instream nitrogen signals to upstream mechanistic landscape processes. Our work can aid in the future interpretation of in-stream concentrations of DOC and DIN as indicators of watershed N-retention status and integrators of watershed hydrobiogeochemical processes

A Comprehensive Assessment of Anthropogenic and Natural Sources and Sinks of Australasia's Carbon Budget

Regional carbon budget assessments attribute and track changes in carbon sources and sinks and support the development and monitoring the efficacy of climate policies. We present a comprehensive assessment of the natural and anthropogenic carbon (C-CO2) fluxes for Australasia as a whole, as well as for Australia and New Zealand individually, for the period from 2010 to 2019, using two approaches: bottom-up methods that integrate flux estimates from land-surface models, data-driven models, and inventory estimates; and top-down atmospheric inversions based on satellite and in situ measurements. Our bottom-up decadal assessment suggests that Australasia's net carbon balance was close to carbon neutral (−0.4 ± 77.0 TgC yr−1). However, substantial uncertainties remain in this estimate, primarily driven by the large spread between our regional terrestrial biosphere simulations and predictions from global ecosystem models. Within Australasia, Australia was a net source of 38.2 ± 75.8 TgC yr−1, and New Zealand was a net CO2 sink of −38.6 ± 13.4 TgC yr−1. The top-down approach using atmospheric CO2 inversions indicates that fluxes derived from the latest satellite retrievals are consistent within the range of uncertainties with Australia's bottom-up budget. For New Zealand, the best agreement was found with a national scale flux inversion estimate based on in situ measurements, which provide better constrained of fluxes than satellite flux inversions. This study marks an important step toward a more comprehensive understanding of the net CO2 balance in both countries, facilitating the improvement of carbon accounting approaches and strategies to reduce emissions

Global nitrous oxide budget (1980--2020)

Nitrous oxide (N2O) is a long-lived potent greenhouse gas and stratospheric ozone-depleting substance that has been accumulating in the atmosphere since the preindustrial period. The mole fraction of atmospheric N2O has increased by nearly 25 % from 270 ppb (parts per billion) in 1750 to 336 ppb in 2022, with the fastest annual growth rate since 1980 of more than 1.3 ppb yr−1 in both 2020 and 2021. According to the Sixth Assessment Report of the Intergovernmental Panel on Climate Change (IPCC AR6), the relative contribution of N2O to the total enhanced effective radiative forcing of greenhouse gases was 6.4 % for 1750–2022. As a core component of our global greenhouse gas assessments coordinated by the Global Carbon Project (GCP), our global N2O budget incorporates both natural and anthropogenic sources and sinks and accounts for the interactions between nitrogen additions and the biogeochemical processes that control N2O emissions. We use bottom-up (BU: inventory, statistical extrapolation of flux measurements, and process-based land and ocean modeling) and top-down (TD: atmospheric measurement-based inversion) approaches. We provide a comprehensive quantification of global N2O sources and sinks in 21 natural and anthropogenic categories in 18 regions between 1980 and 2020. We estimate that total annual anthropogenic N2O emissions have increased 40 % (or 1.9 Tg N yr−1) in the past 4 decades (1980–2020). Direct agricultural emissions in 2020 (3.9 Tg N yr−1, best estimate) represent the large majority of anthropogenic emissions, followed by other direct anthropogenic sources, including fossil fuel and industry, waste and wastewater, and biomass burning (2.1 Tg N yr−1), and indirect anthropogenic sources (1.3 Tg N yr−1) . For the year 2020, our best estimate of total BU emissions for natural and anthropogenic sources was 18.5 (lower–upper bounds: 10.6–27.0) Tg N yr−1, close to our TD estimate of 17.0 (16.6–17.4) Tg N yr−1. For the 2010–2019 period, the annual BU decadal-average emissions for both natural and anthropogenic sources were 18.2 (10.6–25.9) Tg N yr−1 and TD emissions were 17.4 (15.8–19.20) Tg N yr−1. The once top emitter Europe has reduced its emissions by 31 % since the 1980s, while those of emerging economies have grown, making China the top emitter since the 2010s. The observed atmospheric N2O concentrations in recent years have exceeded projected levels under all scenarios in the Coupled Model Intercomparison Project Phase 6 (CMIP6), underscoring the importance of reducing anthropogenic N2O emissions. To evaluate mitigation efforts and contribute to the Global Stocktake of the United Nations Framework Convention on Climate Change, we propose the establishment of a global network for monitoring and modeling N2O from the surface through to the stratosphere. The data presented in this work can be downloaded from https://doi.org/10.18160/RQ8P-2Z4R (Tian et al., 2023)